Unlocking the Potential of Porous Bi2Te3-Based Thermoelectrics Using Precise Interface Engineering through Atomic Layer Deposition.

Porous thermoelectric materials offer exciting prospects for improving the thermoelectric performance by significantly reducing the thermal conductivity. Nevertheless, porous structures are affected by issues, including restricted enhancements in performance attributed to decreased electronic conductivity and degraded mechanical strength. This study introduces an innovative strategy for overcoming these challenges using porous Bi0.4Sb1.6Te3 (BST) by combining porous structuring and interface engineering via atomic layer deposition (ALD). Porous BST powder was produced by selectively dissolving KCl in a milled mixture of BST and KCl; the interfaces were engineered by coating ZnO films through ALD. This novel architecture remarkably reduced the thermal conductivity owing to the presence of several nanopores and ZnO/BST heterointerfaces, promoting efficient phonon scattering. Additionally, the ZnO coating mitigated the high resistivity associated with the porous structure, resulting in an improved power factor. Consequently, the ZnO-coated porous BST demonstrated a remarkable enhancement in thermoelectric efficiency, with a maximum zT of approximately 1.53 in the temperature range of 333-353 K, and a zT of 1.44 at 298 K. Furthermore, this approach plays a significant role in enhancing the mechanical strength, effectively mitigating a critical limitation of porous structures. These findings open new avenues for the development of advanced porous thermoelectric materials and highlight their potential for precise interface engineering through the ALD.

Dual-frequency piezoelectric micromachined ultrasound transducer based on polarization switching in ferroelectric thin films.

Due to its additional frequency response, dual-frequency ultrasound has advantages over conventional ultrasound, which operates at a specific frequency band. Moreover, a tunable frequency from a single transducer enables sonographers to achieve ultrasound images with a large detection area and high resolution. This facilitates the availability of more advanced techniques that simultaneously require low- and high-frequency ultrasounds, such as harmonic imaging and image-guided therapy. In this study, we present a novel method for dual-frequency ultrasound generation from a ferroelectric piezoelectric micromachined ultrasound transducer (PMUT). Uniformly designed transducer arrays can be used for both deep low-resolution imaging and shallow high-resolution imaging. To switch the ultrasound frequency, the only requirement is to tune a DC bias to control the polarization state of the ferroelectric film. Flextensional vibration of the PMUT membrane strongly depends on the polarization state, producing low- and high-frequency ultrasounds from a single excitation frequency. This strategy for dual-frequency ultrasounds meets the requirement for either multielectrode configurations or heterodesigned elements, which are integrated into an array. Consequently, this technique significantly reduces the design complexity of transducer arrays and their associated driving circuits.

Voltage control of magnetism in Fe3-xGeTe2/In2Se3 van der Waals ferromagnetic/ferroelectric heterostructures.

We investigate the voltage control of magnetism in a van der Waals (vdW) heterostructure device consisting of two distinct vdW materials, the ferromagnetic Fe3-xGeTe2 and the ferroelectric In2Se3. It is observed that gate voltages applied to the Fe3-xGeTe2/In2Se3 heterostructure device modulate the magnetic properties of Fe3-xGeTe2 with significant decrease in coercive field for both positive and negative voltages. Raman spectroscopy on the heterostructure device shows voltage-dependent increase in the in-plane In2Se3 and Fe3-xGeTe2 lattice constants for both voltage polarities. Thus, the voltage-dependent decrease in the Fe3-xGeTe2 coercive field, regardless of the gate voltage polarity, can be attributed to the presence of in-plane tensile strain. This is supported by density functional theory calculations showing tensile-strain-induced reduction of the magnetocrystalline anisotropy, which in turn decreases the coercive field. Our results demonstrate an effective method to realize low-power voltage-controlled vdW spintronic devices utilizing the magnetoelectric effect in vdW ferromagnetic/ferroelectric heterostructures.

Nucleation and Layer Closure Behavior of Iridium Films Grown Using Atomic Layer Deposition.

Understanding the initial growth process during atomic layer deposition (ALD) is essential for various applications employing ultrathin films. This study investigated the initial growth of ALD Ir films using tricarbonyl-(1,2,3-η)-1,2,3-tri(tert-butyl)-cyclopropenyl-iridium and O2. Isolated Ir nanoparticles were formed on the oxide surfaces during the initial growth stage, and their density and size were significantly influenced by the growth temperature and substrate surface, which strongly affected the precursor adsorption and surface diffusion of the adatoms. Higher-density and smaller nanoparticles were formed at high temperatures and on the Al2O3 surface, forming a continuous Ir film with a smaller thickness, resulting in a very smooth surface. These findings suggest that the initial growth behavior of the Ir films affects their surface roughness and continuity and that a comprehensive understanding of this behavior is necessary for the formation of continuous ultrathin metal films.

Layer-Controlled Perovskite 2D Nanosheet Interlayer for the Energy Storage Performance of Nanocomposites.

Polymer-based nanocomposites are desirable materials for next-generation dielectric capacitors. 2D dielectric nanosheets have received significant attention as a filler. However, randomly spreading the 2D filler causes residual stresses and agglomerated defect sites in the polymer matrix, which leads to the growth of an electric tree, resulting in a more premature breakdown than expected. Therefore, realizing a well-aligned 2D nanosheet layer with a small amount is a key challenge; it can inhibit the growth of conduction paths without degrading the performance of the material. Here, an ultrathin Sr1.8 Bi0.2 Nb3 O10 (SBNO) nanosheet filler is added as a layer into poly(vinylidene fluoride) (PVDF) films via the Langmuir-Blodgett method. The structural properties, breakdown strength, and energy storage capacity of a PVDF and multilayer PVDF/SBNO/PVDF composites as a function of the thickness-controlled SBNO layer are examined. The seven-layered (only 14 nm) SBNO nanosheets thin film can sufficiently prevent the electrical path in the PVDF/SBNO/PVDF composite and shows a high energy density of 12.8 J cm-3 at 508 MV m-1 , which is significantly higher than that of the bare PVDF film (9.2 J cm-3 at 439 MV m-1 ). At present, this composite has the highest energy density among the polymer-based nanocomposites under the filler of thin thickness.

Breathable MOFs Layer on Atomically Grown 2D SnS2 for Stable and Selective Surface Activation.

2D transition metal dichalcogenides (TMDs) have significant research interests in various novel applications due to their intriguing physicochemical properties. Notably, one of the 2D TMDs, SnS2 , has superior chemiresistive sensing properties, including a planar crystal structure, a large surface-to-volume ratio, and a low electronic noise. However, the long-term stability of SnS2 in humid conditions remains a critical shortcoming towards a significant degradation of sensitivity. Herein, it is demonstrated that the subsequent self-assembly of zeolite imidazolate framework (ZIF-8) can be achieved in situ growing on SnS2 nanoflakes as the homogeneous porous materials. ZIF-8 layer on SnS2 allows the selective diffusion of target gas species, while effectively preventing the SnS2 from severe oxidative degradation. Molecular modeling such as molecular dynamic simulation and DFT calculation, further supports the mechanism of sensing stability and selectivity. From the results, the in situ grown ZIF-8 porous membrane on 2D materials corroborates the generalizable strategy for durable and reliable high-performance electronic applications of 2D materials.

Ultrahigh dielectric permittivity in oxide ceramics by hydrogenation.

Boosting dielectric permittivity representing electrical polarizability of dielectric materials has been considered a keystone for achieving scientific breakthroughs as well as technological advances in various multifunctional devices. Here, we demonstrate sizable enhancements of low-frequency dielectric responses in oxygen-deficient oxide ceramics through specific treatments under humid environments. Ultrahigh dielectric permittivity (~5.2 × 106 at 1 Hz) is achieved by hydrogenation, when Ni-substituted BaTiO3 ceramics are exposed to high humidity. Intriguingly, thermal annealing can restore the dielectric on-state (exhibiting huge polarizability in the treated ceramics) to the initial dielectric off-state (displaying low polarizability of ~103 in the pristine ceramics after sintering). The conversion between these two dielectric states via the ambient environment-mediated treatments and the successive application of external stimuli allows us to realize reversible control of dielectric relaxation characteristics in oxide ceramics. Conceptually, our findings are of practical interest for applications to highly efficient dielectric-based humidity sensors.

Selective Dissolution-Derived Nanoporous Design of Impurity-Free Bi2 Te3 Alloys with High Thermoelectric Performance.

Thermoelectric technology, which has been receiving attention as a sustainable energy source, has limited applications because of its relatively low conversion efficiency. To broaden their application scope, thermoelectric materials require a high dimensionless figure of merit (ZT). Porous structuring of a thermoelectric material is a promising approach to enhance ZT by reducing its thermal conductivity. However, nanopores do not form in thermoelectric materials in a straightforward manner; impurities are also likely to be present in thermoelectric materials. Here, a simple but effective way to synthesize impurity-free nanoporous Bi0.4 Sb1.6 Te3 via the use of nanoporous raw powder, which is scalably formed by the selective dissolution of KCl after collision between Bi0.4 Sb1.6 Te3 and KCl powders, is proposed. This approach creates abundant nanopores, which effectively scatter phonons, thereby reducing the lattice thermal conductivity by 33% from 0.55 to 0.37 W m-1 K-1 . Benefitting from the optimized porous structure, porous Bi0.4 Sb1.6 Te3 achieves a high ZT of 1.41 in the temperature range of 333-373 K, and an excellent average ZT of 1.34 over a wide temperature range of 298-473 K. This study provides a facile and scalable method for developing high thermoelectric performance Bi2 Te3 -based alloys that can be further applied to other thermoelectric materials.

Epitaxial Growth of ß-Ga2O3 Thin Films on Si with YSZ Buffer Layer.

We report the epitaxial growth of (2̅01)-oriented ß-Ga2O3 thin films on a (001) Si substrate using the pulsed laser deposition technique employing epitaxial yttria-stabilized zirconia (YSZ) buffer layers. Epitaxial ß-Ga2O3 thin films possess a biaxial compressive strain on YSZ single-crystal substrates while they exhibit a biaxial tensile strain on YSZ-buffered Si substrates. Post-annealing improves the crystalline quality of ß-Ga2O3 thin films. High-resolution X-ray diffraction analyses reveal that the epitaxial (2̅01) ß-Ga2O3 thin films on Si have eight in-plane domain variants to accommodate the large difference in the crystal structure between monoclinic ß-Ga2O3 and cubic YSZ. The results provide a pathway to integrate epitaxial ß-Ga2O3 thin films on a Si gold standard substrate, which will expand the application scope beyond high-power electronics.

Oxygen scavenging of HfZrO2-based capacitors for improving ferroelectric properties.

HfO2-based ferroelectric (FE) materials have emerged as a promising material for non-volatile memory applications because of remanent polarization, scalability of thickness below 10 nm, and compatibility with complementary metal-oxide-semiconductor technology. However, in the metal/FE/insulator/semiconductor, it is difficult to improve switching voltage (V sw), endurance, and retention properties due to the interfacial layer (IL), which inevitably grows during the fabrication. Here, we proposed and demonstrated oxygen scavenging to reduce the IL thickness in an HfZrO x -based capacitor and the thinner IL was confirmed by cross-sectional transmission electron microscopy. V sw of a capacitor with scavenging decreased by 18% and the same P r could be obtained at a lower voltage than a capacitor without scavenging. In addition, excellent endurance properties up to 106 cycles were achieved. We believe oxygen scavenging has great potential for future HfZrO x -based memory device applications.

Atomically sculptured heart in oxide film using convergent electron beam.

We demonstrate a fabrication of an atomically controlled single-crystal heart-shaped nanostructure using a convergent electron beam in a scanning transmission electron microscope. The delicately controlled e-beam enable epitaxial crystallization of perovskite oxide LaAlO3 grown out of the relative conductive interface (i.e. 2 dimensional electron gas) between amorphous LaAlO3/crystalline SrTiO3.

Wafer-Scale, Conformal, and Low-Temperature Synthesis of Layered Tin Disulfides for Emerging Nonplanar and Flexible Electronics.

Two-dimensional (2D) metal dichalcogenides have drawn considerable interest because they offer possibilities for the implementation of emerging electronics. The emerging electronics are moving toward two major directions: vertical expansion of device space and flexibility. However, the development of a synthesis method for 2D metal dichalcogenides that meets all the requirements remains a significant challenge. Here, we propose a promising method for wafer-scale, conformal, and low-temperature (≤240 °C) synthesis of single-phase SnS2 via the atomic layer deposition technique. There is a trade-off relationship between the crystallinity and orientation preference of SnS2, which is efficiently eliminated by the two-step growth occurring at different temperatures. Consequently, the van der Waals layers of the highly crystalline SnS2 are parallel to the substrate. Thin-film transistors (TFTs) comprising the SnS2 layer show reasonable electrical performances (field-effect mobility: ∼0.8 cm2 V-1 s-1 and on/off ratio: ∼106), which are comparable to that of a single-crystal SnS2 flake. Moreover, we demonstrate nonplanar and flexible TFTs to identify the feasibility of the implementation of future electronics. Both the diagonal-structured TFT and flexible TFT fabricated without a transfer process show electrical performances comparable to those of rigid and planar TFTs. Particularly, the flexible TFT does not exhibit substantial degradation even after 2000 bending cycles. Our work would provide decisive opportunities for the implementation of future electronic devices utilizing 2D metal chalcogenides.

Gate-tunable giant nonreciprocal charge transport in noncentrosymmetric oxide interfaces.

A polar conductor, where inversion symmetry is broken, may exhibit directional propagation of itinerant electrons, i.e., the rightward and leftward currents differ from each other, when time-reversal symmetry is also broken. This potential rectification effect was shown to be very weak due to the fact that the kinetic energy is much higher than the energies associated with symmetry breaking, producing weak perturbations. Here we demonstrate the appearance of giant nonreciprocal charge transport in the conductive oxide interface, LaAlO3/SrTiO3, where the electrons are confined to two-dimensions with low Fermi energy. In addition, the Rashba spin-orbit interaction correlated with the sub-band hierarchy of this system enables a strongly tunable nonreciprocal response by applying a gate voltage. The observed behavior of directional response in LaAlO3/SrTiO3 is associated with comparable energy scales among kinetic energy, spin-orbit interaction, and magnetic field, which inspires a promising route to enhance nonreciprocal response and its functionalities in spin orbitronics.

Precision Interface Engineering of an Atomic Layer in Bulk Bi2Te3 Alloys for High Thermoelectric Performance.

Grafting nanotechnology on thermoelectric materials leads to significant advances in their performance. Creation of structural defects including nano-inclusion and interfaces via nanostructuring achieves higher thermoelectric efficiencies. However, it is still challenging to optimize the nanostructure via conventional fabrication techniques. The thermal instability of nanostructures remains an issue in the reproducibility of fabrication processes and long-term stability during operation. This work presents a versatile strategy to create numerous interfaces in a thermoelectric material via an atomic-layer deposition (ALD) technique. An extremely thin ZnO layer was conformally formed via ALD over the Bi0.4Sb1.6Te3 powders, and numerous heterogeneous interfaces were generated from the formation of Bi0.4Sb1.6Te3-ZnO core-shell structures even after high-temperature sintering. The incorporation of ALD-grown ZnO into the Bi0.4Sb1.6Te3 matrix blocks phonon propagation and also provides tunability in electronic carrier density via impurity doping at the heterogeneous grain boundaries. The exquisite control in the ALD cycles provides a high thermoelectric performance of zT = 1.50 ± 0.15 (at 329-360 K). Specifically, ALD is an industry compatible technique that allows uniform and conformal coating over large quantities of powders. The study is promising in terms of the mass production of nanostructured thermoelectric materials with considerable improvements in performance via an industry compatible and reproducible route.

A novel class of oxynitrides stabilized by nitrogen dimer formation.

Despite the wide applicability of oxynitrides from photocatalysis to refractory coatings, our understanding of the materials has been limited in terms of their thermodynamics. The configurational entropy via randomly mixed O/N or via cation vacancies are known to stabilize oxynitrides, despite the positive formation enthalpies. Here, using tin oxynitrides as a model system, we show by ab initio computations that oxynitrides in seemingly charge-unbalanced composition stabilize by forming pernitrides among metal-(O,N)6 octahedra. The nitrogen pernitride dimer, =(N-N)=, results in the effective charge of -4, facilitating the formation of nitrogen-rich oxynitrides. We report that the dimer forms only in structures with corner-sharing octahedra, since the N-N bond formation requires sufficient rotational degrees of freedom among the octahedra. X-ray photoemission spectra of the synthesized tin oxynitride films reveal two distinct nitrogen bonding environments, confirming the computation results. This work opens the search space for a novel kind of oxynitrides stabilized by N dimer formation, with specific structural selection rules.

Low-temperature wafer-scale synthesis of two-dimensional SnS2.

Research on two-dimensional (2D) metal dichalcogenides is rapidly expanding owing to their unique characteristics that do not exist in bulk materials. The industrially compatible development of these emerging materials is indispensable to facilitate the transition of 2D metal dichalcogenides from the research stage to the practical industrial application stage. However, an industrially relevant method, i.e., the low-temperature synthesis of wafer-scale, continuous, and orientation-controlled 2D metal dichalcogenides, still remains a significant challenge. Here, we report the low-temperature (≤350 °C) synthesis of uniform and continuous n-type SnS2 thin films via the combination of atomic layer deposition (ALD) of tin oxides and subsequent sulfurization. Well-crystallized and aligned SnS2 layers parallel to the substrate are demonstrated through the phase engineering of the ALD-grown tin oxide and the substrate surface. The additional H2S plasma treatment at 300 °C leads to the formation of stoichiometric SnS2. The formation of conformal SnS2 layers over a three-dimensional undulating hole structure is confirmed, which reveals the potential for applications beyond the planar structured architecture. The present results could be a step toward the realization of 2D metal dichalcogenides in industry.

A possible superconductor-like state at elevated temperatures near metal electrodes in an LaAlO3/SrTiO3 interface.

We experimentally investigated the transport properties near metal electrodes installed on a conducting channel in a LaAlO3/SrTiO3 interface. The local region around the Ti and Al electrodes has a higher electrical conductance than that of other regions, where the upper limits of the temperature and magnetic field can be well defined. Beyond these limits, the conductance abruptly decreases, as in the case of a superconductor. The samples with the Ti- or Al-electrode have an upper-limit temperature of approximately 4 K, which is 10 times higher than the conventional superconducting critical temperature of LaAlO3/SrTiO3 interfaces and delta-doped SrTiO3. This phenomenon is explained by the mechanism of electron transfer between the metal electrodes and electronic d-orbitals in the LaAlO3/SrTiO3 interface. The transferred electrons trigger a phase transition to a superconductor-like state. Our results contribute to the deep understanding of the superconductivity in the LaAlO3/SrTiO3 interface and will be helpful for the development of high-temperature interface superconductors.

Mechanically Robust, Stretchable Solar Absorbers with Submicron-Thick Multilayer Sheets for Wearable and Energy Applications.

A facile method to fabricate a mechanically robust, stretchable solar absorber for stretchable heat generation and an enhanced thermoelectric generator (TEG) is demonstrated. This strategy is very simple: it uses a multilayer film made of titanium and magnesium fluoride optimized by a two-dimensional finite element frequency-domain simulation, followed by the application of mechanical stresses such as bending and stretching to the film. This process produces many microsized sheets with submicron thickness (∼500 nm), showing great adhesion to any substrates such as fabrics and polydimethylsiloxane. It exhibits a quite high light absorption of approximately 85% over a wavelength range of 0.2-4.0 µm. Under 1 sun illumination, the solar absorber on various stretchable substrates increased the substrate temperature to approximately 60 °C, irrespective of various mechanical stresses such as bending, stretching, rubbing, and even washing. The TEG with the absorber on the top surface also showed an enhanced output power of 60%, compared with that without the absorber. With an incident solar radiation flux of 38.3 kW/m2, the output power significantly increased to 24 mW/cm2 because of the increase in the surface temperature to 141 °C.

Nonlocal Spin Diffusion Driven by Giant Spin Hall Effect at Oxide Heterointerfaces.

A two-dimensional electron gas emerged at a LaAlO3/SrTiO3 interface is an ideal system for "spin-orbitronics" as the structure itself strongly couple the spin and orbital degree of freedom through the Rashba spin-orbit interaction. One of core experiments toward this direction is the nonlocal spin transport measurement, which has remained elusive due to the low spin injection efficiency to this system. Here we bypass the problem by generating a spin current not through the spin injection from outside but instead through the inherent spin Hall effect and demonstrate the nonlocal spin transport. The analysis on the nonlocal spin voltage, confirmed by the signature of a Larmor spin precession and its length dependence, displays that both D'yakonov-Perel' and Elliott-Yafet mechanisms involve in the spin relaxation at low temperature. Our results show that the oxide heterointerface is highly efficient in spin-charge conversion with exceptionally strong spin Hall coefficient γ ∼ 0.15 ± 0.05 and could be an outstanding platform for the study of coupled charge and spin transport phenomena and their electronic applications.

Harman Measurements for Thermoelectric Materials and Modules under Non-Adiabatic Conditions.

Accuracy of the Harman measurement largely depends on the heat transfer between the sample and its surroundings, so-called parasitic thermal effects (PTEs). Similar to the material evaluations, measuring thermoelectric modules (TEMs) is also affected by the PTEs especially when measuring under atmospheric condition. Here, we study the correction methods for the Harman measurements with systematically varied samples (both bulk materials and TEMs) at various conditions. Among several PTEs, the heat transfer via electric wires is critical. Thus, we estimate the thermal conductance of the electric wires, and correct the measured properties for a certain sample shape and measuring temperature. The PTEs are responsible for the underestimation of the TEM properties especially under atmospheric conditions (10-35%). This study will be useful to accurately characterize the thermoelectric properties of materials and modules.